Process for breaking petroleum emulsions



UNITED STATES PATENT OFFICE rnocass Foa BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, Mo., assignor to Tretolite Company, Webster Groves. Mm, a corporation of Missouri No Drawing. Application October 9, 1933,

Serial No. 692,904

11 Claims. (Cl. 196-4) This invention relates to the treatment of emulsulfuric acid molecule is split off when reaction sions of mineral oil and water, such as petroleum occurs between the acid sulfate and another emulsions, for the purpose of separating the oil hydrogen of the nucleus, wherebyapropyl radical from the water. 1 I or residue is introduced into the nucleus. An-

Petroleum emulsions are of the water -in-oil other procedure contemplates the passage of an 5 type, and comprise fine droplets of naturallyolefine, such as propylene, into naphthalene suloccurring waters or brines, dispersed in a more fonic acid, or naphthalene, dissolved in an excess or less permanent state throughout the oil which of sulfuric acid. Other reactions might involve constitutes the continuous phase of the emulsion. the use of propyl chloride with the splitting of They are obtained from producing wells and from hydrochloric acid. The reactions involving in- 10 the bottoms of oil storage tanks, and are comtroduction of a hydroaromatic residue are identimonly referred to as "Cut oil, Roily oil, cal with those involving propyl alcohol or "Emulsified oil and Bottom settlings. propylene. The treating agent contemplated by The object of my invention is to provide a novel, 'my process is one in which the residue introduced inexpensive and eflicient process for separating into the aromatic is derived from a reactive emulsions of the kind referred to into their comhydroaromatic of a kind to be subsequently deponent parts of oil and water or brine. scribed.

Briefly described my process consists in 'sub- Hexahydrobenzene is the parent hydrocarbon jecting a petroleum emulsion of the water-in-oil of the hydroaromatic substances. Tetra and di- 2 type, to the action of a'treating agent or demulsihydrobenzene bear the same relationship to it, fying agent of a particular kind or composition that an olefine and a dioleflne show to the hereinafter described, thereby causing the emulparaflin, having the same number of carbon sion to break down and separate into its comatoms. Hexahydrobenzenes are the aromatic ponent parts of oil and water or brine, when the members of the cycloparaflins and are relatively emulsion is permitted to remain in a quiescent inactive. However, certain hydroaromatic hy- 25 state after such treatment, or when subjected to drocarbcns, such as tetrahydrobenzene and other equivalent separatory procedure. the dihydrobenzene have a chemical activity com- The treating agent or demulsifying agent used parable to the cyclo-olefines and the cyclo-diolein my process consists of a substituted aromatic fines. Such materials are considered as reactive '30 sulfonic acid in which a reactive hydroaromatic hydroaromatic compounds or reactive hydroresidue derived from a hydroaromatic alcohol or aromatic hydrocarbons. Indeed, hydroaromatic hydroaromatic hydrocarbon has been substituted compounds, such as dihydrobenzene, may be so in the aromatic nucleus. Such hydroaromatic violently reactive-that there is a tendency to residues, just like ordinary aliphatic residues, may polymerize in preference to entering the arcbe introduced into a. sulfo-aromatic nucleus, or matic nucleus when dihydrobenzene is condensed 35 else the sulfonic group may be introduced into with an aromatic, such as naphthalene. Just as the aromatic nucleus simultaneously with the propyl alcohol is reactive towards sulfuric acid, introduction of the hydroaromatic residue, or, there are suitable hydroaromatic alcohols which if one desires, the aromatic compound, after will combine with sulfuric acid, and these are introduction of the hydroaromatic residue, may considered as being reactive. These reactive 4t be sulionated. The processes employed for prohydroaromatic alcohols may be condensed with ducing such chemical compounds are well known, an aromatic compound just as readily as a rebeing the same as the ones more frequently emactive hydroaromatic hydrocarbon of the olefine ployed in the manufacture of similar products or diolefine type may be condensed therewith.

from aromatic compounds and either aliphatic ,Examples, of such reactive hydroaromatic alco- 4E alcohols or aliphatic hydrocarbons. hols include cyclohexanol, methyl cyclohexanol, In manufacturing this type of reagent, one well dimethylcyclohexanol, trimethylcyclohexanol, known procedure is to convert an alcohol such .etc. Some of these hydroaromatic compounds as pr pyl alcoho r i pr p l oh l, i pr pyl appear in various isomeric forms. Substantially hydrogen sulfate. Said latter material is reany isomeric form is suitable. Some of these 5( acted with an aromatic compound, such as naphhydroaromatic alcohols are produced by the thalene, in the presence of an excess of a sulfonathydrogenation of phenol, cresol, beta naphthol, ing agent, such as sulfuric acid. As a result, suletc.

,furic acid reacts at a hydrogen of the aromatic The aromatic compound employed in produc- 56 nucleus to produce a sulfonic acid; and also a ing the treating agent contemplated by my proc- T is a hydrogen atom'thereof or a substituent group or atom, such as a hydroxyl group or a halogen atom, H80: is the conventional sulfonic acid residue, and R is the reactive hydroaromatic res-v idue derived from a hydroaromatic olefine, suchas cyclohexine CsHio, or a hydroaromatic diolefine, or a hydroaromatic alcohol. R. may be derived from a monocyclic body. such as benzol or phenol, or, as previously stated, from a polycyclic material, such as naphthalene or hydroxy naphthalene.

The hydrogen of the sulfonic acid may be replaced by any suitable equivalent, such as a sodium, potassium, calcium, or magnesium atom; it may be replaced by an ammonium radical, or by a radical derived from a basic amine, such as triethanolamine. The hydrogen'may be replaced by an organic radical, such as the ethyl group, etc. The formula above stated may be rewritten as R.T.Z.SOa.R', in which the symbols have their previous significance and Z represents the hydrogen ion equivalent of the sulfonic acid, as previously described. Some of the reagents of this class are water-soluble; some are oil-soluble; some are soluble in both oil and water, and some are only sparingly soluble in either oil or water. Some of the reagents in water-soluble form, such as in the form of an ammonium salt, react with soluble calcium solutions and soluble magnesium solutions to produce precipitates. Such reagents, characterized by insoluble alkaline earth salts, appear to be most effective for breaking oil field emulsions and are preferable for use in the present process. The sulfonic acid body may contain more than one sulfo radical. Naphthalene disulfonic acid may furnish the aromatic nucleus.

Possibly a sulfonic radical or other substituent' member could be introduced into the hydroaromatic residue.

My preferred treating agent or demulsifying agent is obtained by mixing approximately 130 parts of naphthalene with approximately 100 parts of hexahydrophenol (sometimes referred to under the trade name of Hexalin) and adding approximately 400 parts of 66 Baum sulfuric acid. The sulfuric acid is added slowly so that the reaction takes place within the limit of 60 to 90 centigrade. When the reaction is completed and the temperature has dropped to less than 30 0., approximately 500 parts of water are added and mixed in, so that the entire reaction mass is dissolved, or, is at least, homogeneous. This aqueous mixture is allowed to stand until a relatively complete separation takes place. The lower dilute acid layer is withdrawn. The upper acid mass may be used as such, or may be neutralized with various hydroxides, carbonates, etc. to give the salts previously mentioned. The water-soluble salts, such as the sodium salts, may be reacted with water-soluble iron salts, copper salts, etc. to give the corresponding heavy metal salt, by metathesis. Esters may be formed in the conventional manner. Triethanolamine may be used as the neutralizing agent. I prefer to new tralize the acidic mass with strong ammonium hydroxide. Such a reagent produces precipitates in the presence of soluble alkaline earth salts.

of petroleum emulsions.

In practising my process, a treating agent or demulsifying agent of the kind above described may be brought in contact with the emulsion to be treated in any of the numerous ways now employed in the treatment of petroleum emulsions of the water-in-oil type with chemical demulsii'ying agents, such, for example, as by introducing the treating agent into the well in which the emulsion is produced; introducing the treating agent into a conduit through which the emulsion is flowing; introducing the treating agent into a tank in which the emulsion is stored; or introducing the treating agent into a container that holds a sludge obtained from the bottom of an oil storage tank. In some instances, it maybe advisable to introduce the treating agent into a producing well in such a way that it will become mixed with water and oil that are emerging from the surrounding strata, before said water and oil enter the barrel of the well pump or the tubing up through which said water and oil flow to the surface of the ground. After treatment, the emulsion is allowed to stand in a quiescent state, usually in a settling tank, and usually at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough to prevent the volatilization of valuable constituents of the oil. If desired, the treated emulsion may be acted upon by one or more of the various kinds of apparatus now used in the operation of breaking petroleum emulsions, such as homogenizers, hay tanks. gun barrels, filters, centrifuges, or electrical dehydrators.

The amount of treating agent that may be required to break the emulsion may vary from approximately 1 part of treating agent to 500 parts of emulsion, up to 1 part of treating agent to 20,000 or even 30,000 parts of emulsion. I The proportion depends on the type of emulsion being 7 treated, and also upon the'equipment being used, and the temperature employed. In treating exceptionally refractory emulsions of the kind known as tank bottoms and residual pit oils, the ratio of 1: 500, above referred to, may be required. In treating fresh emulsions, i. e., emulsions that will yield readily to the action of chemclaim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulfonic acid body of the type R.T.Z,SOa.R, in which R is an aromatic residue, T is a hydrogen atom thereof or a substituent atom or a hydroxyl group, Z is the hydrogen ion equivalent of the sulfonic acid, S is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue.

2. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO:.R', in which R is a monocyclic aromatic residue, T is a hydrogen atom thereof or a substituent atom or a hydroxyl group, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue.

3. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demul sifying agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO3.R, in which R is a polycyclic aromatic residue, T is a hydrogen atom thereof or a substituent atom or a hydroxyl group, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R. is a reactive hydroaromatic residue.

4. A process for breaking petroleum emulsions of thewater-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO3.R', in which R is a bicyclic aromatic residue, T is a hydrogen atom thereof or a substituent atom or a hydroxyl group, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulionic acid residue, and R is a reactive hydroaro- 2 is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue.

6. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulionic acid body of the type R.T.ZSO3.R, in which R is a naphthalene residue, T is a hydrogen atom thereof or a substituent atom or a hydroxyl group, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue, and being further characterized by being capable of forming a precipitate when reacted with a soluble alkaline earth salt.

7. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO3.R', in which R- is the naphthalene residue CioHs, T is a hydrogen atom, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue derived from a hydroaromatic alcohol.

8. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO:.R', in which R is the naphthalene residue Ciel-15,71 is a hydrogen atom, Z is the hydrogen ion equivalent of the sulfonic acid, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue derived from cyclohexanol.

9. A process for breaking petroleum emulsions of the water-in-oil type, which consistsin subjecting the emulsion to the action of a demulsifying agent containing a substituted aromatic sultonic acid body of the type R.T.ZSO3.R', in which R is the naphthalene residue CroHs, T is a hydrogen atom, Z represents an ammonium radical, S0: is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue derived from cyclohexanol.

10. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsify ing agent containing a substituted aromatic sulfonic acid body of the type R.T.ZSO3.R, in which R is the naphthalene aromatic residue CH5, T is a hydrogen atom, Z represents an ammonium radical, S03 is the conventional sulfonic acid residue, and R is a reactive hydroaromatic residue derived from cyclohexanol, and being further characterized by being capable of forming a precipitate when reacted with a soluble alkaline earth salt.

11. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifying agent produced by reacting molecular proportions of naphthalene and cyclohexanol with a large excess of strong sulfuric acid, followed by a washing process and a neutralization process by means of strong ammonia.

MELVIN DE GROOTE. 

